Process for preparing acrylate compound

ABSTRACT

An acrylate compound of formula (4):  
                 
 
is produced by allowing an acrylic acid compound of formula (1):  
                 
 
to react with an unsaturated compound of formula (2) or (3):  
                 
 
     In formulae (1) through (4), R 1  and R 2  are H or F, R 3  is H, F, or an alkyl, alkenyl, fluoroalkyl or fluoroalkenyl group, R 4  and R 5  are H, halogen, or an alkyl, alkenyl, halogenated alkyl or halogenated alkenyl group; and X and Y are an unsubstituted or substituted hydrocarbon group, and dashed line - - - means that X and Y may be bonded together to form a cyclic structure.

BACKGROUND OF THE INVENTION

(1) Field of the Invention

This invention relates to a process for preparing an acrylate compoundwhich is expected to be used as a raw material for functional polymers,pharmaceuticals and pesticides.

(2)Description of the Related Art

In recent years acrylate compounds have provided a great attraction, forexample, as monomers used for producing a resist for advancedsemiconductor lithography. Especially acrylate compounds having atertiary ester skeletal structure capable of being dissociated with anacid are suitable therefor in view of lithography mechanism.

As specific examples of the acrylate or methacrylate compounds havingsuch a skeletal structure capable of being dissociated with an acid,there can be mentioned acrylates and methacrylates having anacid-dissociatable group such as a 2-methyl-2-adamantyl group or a8-ethyl-8-tricyclodecanyl group (Japanese Unexamined Patent Publication[hereinafter abbreviated to “JP-A”) No. 2001-188352, JP-AH11-305444andJP-AH9-43848), and α-trifluoromethylacrylates having anacid-dissociatable group such as a 2-methyl-2-adamantyl group or a1-alkyl-1-cycloalkyl group (JP-A 2001-302728).

The above-mentioned acrylate compounds are prepared, for example, by thefollowing known processes.

A first type process comprises allowing an acrylic acid chloridecompound to react with an alcohol or a metal alcoholate in the presenceof a base. The first type process includes, for example, a processwherein 2-methyl-2-adamantanol is allowed to react with acryloylchloride or methacryloyl chloride in the presence of triethylamine togive a corresponding acrylate or methacrylate compound (for example,JP-A H11-305444, JP-A 2000-122294, JP-A 2000-229911 and JP-A2001-188352), and a process wherein 8-ethyl-8-cyclododecanol is allowedto react with methacryloyl chloride in the presence of triethylamine(JP-A 2001-188352). The first type process further includes a processwherein 2-adamantanone is allowed to react with methyllithium or amethyl Grignard reagent to give a Li or Mg salt of2-methyl-2-adamantanonol, and then, methacryloyl chloride is added in asolution of the thus-obtained Li or Mg salt to give a correspondingmethacrylate compound (JP-A H10-182552 and JP-A 2000-229911).

The first type process has a problem such that acryloyl chloride andmethacryloyl chloride are not readily available and are expensive, andare difficult to handle because these acid chlorides easily produce alarge amount of hydrogen chloride gas when they are contacted withmoisture in the air.

As a process wherein acryloyl chloride and methacryloyl chloride are notused to overcome the first type process, a second process has beenproposed which includes, for example, a process wherein acrylic acid isallowed to react with a tertiary alcohol such as 1-ethyl-1-cyclohexanol(JP-A 2000-319226).

However, in the second process, large amounts of a carboxylic acidanhydride such as acetic anhydride and an amine compound such astriethylamine must be used to smoothly carry out the reaction, with theresult of reduction in efficiency and cost for production.

SUMMARY OF THE INVENTION

In view of the foregoing, a primary object of the present invention isto provide a process for preparing acrylate compounds whereby the objectcompounds can be prepared with high efficiency without theabove-mentioned problems of the prior art, namely, with a reduced costand an enhanced safety.

Thus, in accordance with the present invention, there is provided aprocess for preparing an acrylate compound represented by the followingformula (4):

wherein R¹ and R²independently represent a hydrogen atom or a fluorineatom, R³represents a hydrogen atom, a fluorine atom, an alkyl group, analkenyl group, a fluoroalkyl group, or a fluoroalkenyl group, R⁴ and R⁵independently represent a hydrogen atom, a halogen atom, an alkyl group,an alkenyl group, a halogenated alkyl group, or a halogenated alkenylgroup; and X and Y independently represent a hydrocarbon group, whichmay have at least one substituent selected from the group consisting ofa halogen-containing substituent, an oxygen-containing substituent and anitrogen-containing substituent, and dashed line - - - means that X andY may be bonded together to form a cyclic structure;

-   -   which comprises allowing an acrylic acid compound represented by        the following formula (1):        wherein R¹, R² and R³ are the same as defined above for formula        (4), to react with an unsaturated compound represented by the        following formula (2) or (3):        wherein R⁴, R⁵, X and Y are the same as defined above for        formula (4).

DESCRIPTION OF THE PREFERRED EMBODIMENT

The acrylic acid compound used as a raw material in the process of thepresent invention is represented by the above formula (1). In formula(1), R¹ and R² independently represent a hydrogen atom or a fluorineatom, and preferably represent a hydrogen atom.

In formula (1), R³ represents a hydrogen atom, a fluorine atom, an alkylgroup, an alkenyl group, a fluoroalkyl group or a fluoroalkenyl group.R³ is preferably selected from a hydrogen atom, a fluorine atom, a C₁-C₄straight-chain or branched alkyl group, a C₂-C₄ straight-chain orbranched alkenyl group, a C₁-C₄ straight-chain or branched fluoroalkylgroup, and a C₂-C₄ straight-chain or branched fluoroalkenyl group. Asspecific examples of the alkyl group, there can be mentioned methyl,ethyl, propyl and butyl groups. As specific examples of the alkenylgroup, there can be mentioned ethenyl, 1-propenyl, allyl and 1-, 2- or3-butenyl groups. As specific examples of the fluoroalkyl group, therecan be mentioned fluoromethyl, fluoroethyl, fluoropropyl and fluorobutylgroups. As specific examples of the fluoroalkenyl group, there can bementioned fluoroethenyl, fluoro-1-propenyl, fluoroallyl andfluoro-1-butenyl, fluoro-2-butenyl and fluoro-3-butenyl groups.

Preferable examples of the acrylic acid compound of formula (1) arethose wherein R¹ and R² are a hydrogen atom, and R³ is selected from ahydrogen atom, a fluorine atom, an alkyl group (preferably a C₁-C₄straight-chain or branched alkyl group), an alkenyl group (preferably aC₂-C₄ straight-chain or branched alkenyl group), a fluoroalkyl group(preferably a C₁-C₄ straight-chain or branched fluoroalkyl group) and afluoroalkenyl group (preferably a C₂-C₄ straight-chain or branchedfluoroalkenyl group).

As specific examples of the acrylic acid compound, there can bementioned acrylic acid, methacrylic acid, α-ethylacrylic acid,α-n-propylacrylic acid, α-isopropylacrylic acid, α-n-butylacrylic acid,α-isobutylacrylic acid, α-s-butylacrylic acid, α-allylacrylic acid,α-t-butylacrylic acid, α-fluoromethylacrylic acid,α-trifluoromethylacrylic acid, α-fluoroacrylic acid, α-difluoroacrylicacid, α-trifluoroacrylic acid, α-fluoroethylacrylic acid,α-difluoroethylacrylic acid, α-trifluoroethylacrylic acid,α-tetrafluoroethylacrylic acid, α-perfluoroethylacrylic acid,α-fluoropropylacrylic acid, α-difluoropropylacrylic acid,α-trifluoropropylacrylic acid, α-tetrafluoropropylacrylic acid,α-pentafluoropropylacrylic acid, α-hexafluoropropylacrylic acid,α-perfluoropropylacrylic acid, α-fluorobutylacrylic acid,α-difluorobutylacrylic acid, α-trifluorobutylacrylic acid,α-tetrafluorobutylacrylic acid, α-pentafluorobutylacrylic acid,α-hexafluorobutylacrylic acid, α-heptafluorobutylacrylic acid,α-octafluorobutylacrylic acid, α-perfluorobutylacrylic acid,α-fluoroallylacrylic acid, α-difluoroallylacrylic acid,α-trifluoroallylacrylic acid, α-tetrafluoroallylacrylic acid,α-perfluoroallylacrylic acid, α-trifluoromethyl-α-fluoroacrylic acid,α-trifluoromethyl-β,β-difluoroacrylic acid and α,β,β-trifluoroacrylicacid.

Of these, a-trifluoromethylacrylic acid, α-trifluoroethylacrylic acid,α-perfluoroethylacrylic acid, α-perfluoropropylacrylic acid,α-perfluorobutylacrylic acid, α-fluoroacrylic acid, acrylic acid andmethacrylic acid are preferable. α-trifluoromethylacrylic acid, acrylicacid and methacrylic acid are especially preferable.

The unsaturated compound used as a raw material in the process of thepresent invention is represented by the formula (2) or (3), which has atleast one carbon-carbon double bond in the structure and at least onecarbon atom of the carbon-carbon double bond is bonded to only carbonatoms, namely, is not directly bonded to any atom other than carbonatom. The skeleton of the unsaturated compound may be either achain-like structure including a straight chain structure and a branchedstructure, or an alicyclic structure.

The above-mentioned unsaturated compound of formula (2) or (4) includes,for example, those which are represented by the following formulae (7)through (13).

Compounds represented by the following formula (7):

wherein R⁷and R⁸ independently represent a hydrogen atom, a halogenatom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, and R⁹ and R¹⁰ independently represent a C₁-C₁₀straight-chain or branched alkyl group, or a C₂-C₁₀ straight-chain orbranched alkenyl group;

-   -   compounds represented by the following formula (8):        wherein R⁷and R⁸ independently represent a hydrogen atom, a        halogen atom, a C₁-C₄ straight-chain or branched alkyl group, a        C₂-C₄ straight-chain or branched alkenyl group, a C₁-C₄        straight-chain or branched haloalkyl group, or a C₂-C₄        straight-chain or branched haloalkenyl group, and R¹¹ and R¹²        independently represent a C₁-C₁₀ straight-chain or branched        alkyl group, or a C₂-C₁₀ straight-chain or branched alkenyl        group;    -   compounds represented by the following formula (9):        wherein R⁷and R⁸ independently represent a hydrogen atom, a        halogen atom, a C₁-C₄ straight-chain or branched alkyl group, a        C₂-C₄ straight-chain or branched alkenyl group, a C₁-C₄        straight-chain or branched haloalkyl group, or a C₂-C₄        straight-chain or branched haloalkenyl group, and R¹³ represents        a C₂-C₁₅ straight-chain or branched alkylene group or a C₂-C₁₅        straight-chain or branched alkenylene group;    -   compounds represented by the following formula (10):        wherein R⁷ and R⁸ independently represent a hydrogen atom, a        halogen atom, a C₁-C₄ straight-chain or branched alkyl group, a        C₂-C₄ straight-chain or branched alkenyl group, a C₁-C₄        straight-chain or branched haloalkyl group, or a C₂-C₄        straight-chain or branched haloalkenyl group, and R¹⁴ represents        a C₁-C₁₅ alkylene group, or a C₂-C₁₅ alkenylene group;    -   compounds represented by the following formula (11):        wherein R⁷and R⁸ independently represent a hydrogen atom, a        halogen atom, a C₁-C₄ straight-chain or branched alkyl group, a        C₂-C₄ straight-chain or branched alkenyl group, a C₁-C₄        straight-chain or branched haloalkyl group, or a C₂-C₄        straight-chain or branched haloalkenyl group, R¹⁵ represents a        C₁-C₁₅ alkylene group or a C₂-C₁₅ alkenylene group, and R¹⁶        represents a C₁-C₃ alkylene group;    -   compounds represented by the following formula (12):        wherein R⁷and R⁸ independently represent a hydrogen atom, a        halogen atom, a C₁-C₄ straight-chain or branched alkyl group, a        C₂-C₄ straight-chain or branched alkenyl group, a C₁-C₄        straight-chain or branched haloalkyl group, or a C₂-C₄        straight-chain or branched haloalkenyl group, R¹⁷ represents a        C₁-C,₅ alkylene group or a C₂-C₁₅ alkenylene group, and R¹⁸        represents a C₁-C₃ alkylene group; and    -   compounds represented by the following formula (13):        wherein R⁷and R⁸ independently represent a hydrogen atom, a        halogen atom, a C₁-C₄ straight-chain or branched alkyl group, a        C₂-C₄ straight-chain or branched alkenyl group, a C₁-C₄        straight-chain or branched haloalkyl group, or a C₂-C₄        straight-chain or branched haloalkenyl group, and R¹⁹ and R²⁰        independently represent a hydrogen atom, a C₁-C₄ straight-chain        or branched alkyl group, a C₂-C₄ straight-chain or branched        alkenyl group, a C₁-C₄ straight-chain or branched haloalkyl        group, a C₂-C₄ straight-chain or branched haloalkenyl group, a        hydroxyl group, a C₁-C₄ alkoxy group, an amino group, a carboxyl        group, an ester group, a carbonyl group or a halogen atom.

As examples of the unsaturated compound of the above formula (9), therecan be mentioned those which are represented by the following formulae(14) through (20).

-   -   Compounds represented by the following formula (14):        wherein R⁷and R⁸ independently represent a hydrogen atom, a        halogen atom, a C₁-C₄ straight-chain or branched alkyl group, a        C₂-C₄ straight-chain or branched alkenyl group, a C₁-C₄        straight-chain or branched haloalkyl group, or a C₂-C₄        straight-chain or branched haloalkenyl group, and R²¹        independently represents a C₁-C₄ straight-chain or branched        alkyl group, a C₂-C₄ straight-chain or branched alkenyl group, a        C₁-C₄ straight-chain or branched haloalkyl group, a C₂-C₄        straight-chain or branched haloalkenyl group, a hydroxyl group,        a C₁-C₄ alkoxy group, an amino group, a carboxyl group, an ester        group, a carbonyl group or a halogen atom, and n is an integer        in the range of 0 to 8;    -   compounds represented by the following formula (15):        wherein R^(7,) R⁸ and R²¹ are the same as defined above for        formula (14), and n is an integer in the range of 0 to 10;    -   compounds represented by the following formula (16):        wherein R^(7,) R⁸ and R²¹ are the same as defined above for        formula (14), and n is an integer in the range of 0 to 6;    -   compounds represented by the following formula (17):        wherein R⁷, R⁸ and R²¹ are the same as defined above for formula        (14), and n is an integer in the range of 0 to 8;    -   compounds represented by the following formula (18):        wherein R⁷, R⁸ and R²¹ are the same as defined above for formula        (14), and n is an integer in the range of 0 to 6;    -   compounds represented by the following formula (19):        wherein R⁷, R⁸ and R²¹ are the same as defined above for formula        (14), and n is an integer in the range of 0 to 8; and    -   compounds represented by the following formula (20):        wherein R⁷, R⁸ and R²¹ are the same as defined above for formula        (14), and n is an integer in the range of 0 to 8.

As examples of the unsaturated compound of the above formula (10), therecan be mentioned those which are represented by the following formulae(21) through (27).

Compounds represented by the following formula (21):

wherein R⁷ and R⁸ independently represent a hydrogen atom, a halogenatom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, and R²¹ independently represents a C₁-C₄straight-chain or branched alkyl group, a C₂-C₄ straight-chain orbranched alkenyl group, a C₁-C₄ straight-chain or branched haloalkylgroup, a C₂-C₄ straight-chain or branched haloalkenyl group, a hydroxylgroup, a C₁-C₄ alkoxy group, an amino group, a carboxyl group, an estergroup, a carbonyl group or a halogen atom, and n is an integer in therange of 0 to 7;

-   -   compounds represented by the following formula (22):        wherein R⁷, R⁸ and R²¹ are the same as defined above for formula        (21), and n is an integer in the range of 0 to 9;    -   compounds represented by the following formula (23):        wherein R⁷, R⁸ and R²¹ are the same as defined above for formula        (21), and n is an integer in the range of 0 to 5;    -   compounds represented by the following formula (24):        wherein R⁷, R⁸ and R²¹ are the same as defined above for formula        (21), and n is an integer in the range of 0 to 7;    -   compounds represented by the following formula (25):        wherein R⁷, R⁸ and R²¹ are the same as defined above formula        (21), and n is an integer in the range of 0 to 5;    -   compounds represented by the following formula (26):        wherein R⁷, R⁸ and R²¹ are the same as defined above for formula        (21), and n is an integer in the range of 0 to 7; and    -   compounds represented by the following formula (27):        wherein R⁷, R⁸ and R²¹ are the same as defined above for formula        (21), and n is an integer in the range of 0 to 7.

Among the unsaturated compounds of formula (22), 1-ethylcyclohexenerepresented by the following formula (36) is especially preferable.

As examples of the unsaturated compound of the above formula (11), therecan be mentioned those which are represented by the following formulae(28) through (31).

Compounds represented by the following formula (28):

wherein R⁷ and R⁸ independently represent a hydrogen atom, a halogenatom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, and R²¹ independently represents a C₁-C₄straight-chain or branched alkyl group, a C₂-C₄ straight-chain orbranched alkenyl group, a C₁-C₄ straight-chain or branched haloalkylgroup, a C₂-C₄ straight-chain or branched haloalkenyl group, a hydroxylgroup, a C₁-C₄ alkoxy group, an amino group, a carboxyl group, an estergroup, a carbonyl group or a halogen atom, and n is an integer in therange of 0 to 8;

-   -   compounds represented by the following formula (29):        wherein R^(7,) R⁸ and R²¹ are the same as defined above for        formula (28), and n is an integer in the range of 0 to 8;    -   compounds represented by the following formula (30):        wherein R⁷, R⁸ and R²¹ are the same as defined above for formula        (28), n is an integer in the range of 0 to 5, R independently        represents a C₁-C₄ straight-chain or branched alkyl group, a        C₂-C₄ straight-chain or branched alkenyl group, a C₁-C₄        straight-chain or branched haloalkyl group, a C₂-C₄        straight-chain or branched haloalkenyl group, a hydroxyl group,        a C₂-C₄ alkoxy group, an amino group, a carboxyl group, an ester        group, a carbonyl group or a halogen atom, and m is an integer        in the range of 0 to 8; and,    -   compounds represented by the following formula (31):        wherein R^(7,) R⁸, R²¹ and R²² are the same as defined above for        formulae (28) and (30), and n is an integer in the range of 0 to        5, and m is an integer in the range of 0 to 8.

As examples of the unsaturated compound of the above formula (12), therecan be mentioned those which are represented by the following formulae(32) through (35).

Compounds represented by the following formula (32):

wherein R⁷and R⁸ independently represent a hydrogen atom, a halogenatom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, and R²¹ independently represents a C₁-C₄straight-chain or branched alkyl group, a C₂-C₄ straight-chain orbranched alkenyl group, a C₁-C₄ straight-chain or branched haloalkylgroup, a C₂-C₄ straight-chain or branched haloalkenyl group, a hydroxylgroup, a C₁-C₄ alkoxy group, an amino group, a carboxyl group, an estergroup, a carbonyl group or a halogen atom, and n is an integer in therange of 0 to 8;

-   -   compounds represented by the following formula (33):        wherein R⁷, R⁸ and R²¹ are the same as defined above for formula        (32), and n is an integer in the range of 0 to 8;    -   compounds represented by the following formula (34):        wherein R⁷, R⁸ and R²¹ are the same as defined above for formula        (32), n is an integer in the range of 0 to 5, R²² independently        represents a C₁-C₄ straight-chain or branched alkyl group, a        C₂-C₄ straight-chain or branched alkenyl group, a C₁-C₄        straight-chain or branched haloalkyl group, a C₂-C₄        straight-chain or branched haloalkenyl group, a hydroxyl group,        a C₁-C₄ alkoxy group, an amino group, a carboxyl group, an ester        group, a carbonyl group or a halogen atom, and m is an integer        in the range of 0 to 8; and,    -   compounds represented by the following formula (35):        wherein R⁷, R⁸ , R²¹ and R²² are the same as defined above for        formulae (32) and (34), and n is an integer in the range of 0 to        8, and m is an integer in the range of 0 to 8.

Among the unsaturated compounds of formula (13), 2-methyleneadamantanerepresented by the following formula (37) is especially preferable.

In R^(7,) R⁸ and R¹⁹ to R²² of the above formulae (7) to (35), the terms“C₁-C₄ straight-chain or branched haloalkyl group” and “C₂-C₄straight-chain or branched haloalkenyl group” mean a C₁-C₄straight-chain or branched alkyl group and a C₂-C₄ straight-chain orbranched alkenyl group, each having one or more halogen substituents,respectively. The halogen substituent includes chlorine, bromine, iodineand fluorine. The term “halogen atom” in R^(7,) R⁸ and R¹⁹ to R²² of theformulae (7) to (35) means chlorine, bromine, iodine and fluorine atoms.

The unsaturated compounds of formulae (2) and (3) used in the process ofthe present invention can be easily prepared, for example, by a methodwherein a commercially available corresponding tertiary alcohol issubjected to intramolecular dehydration reaction, or a method wherein acommercially available corresponding carbonyl compound is subjected toWittig reaction.

The amount of the unsaturated compound of formula (2) or (3) used in theprocess of the present invention is not particularly limited, but ispreferably in the range of 1 mol to 20 mols per mol of the acrylic acidcompound (1). When the amount of the unsaturated compound is too small,the conversion of the acrylic acid compound tends to be poor. Incontrast, when the amount of the unsaturated compound is too large, theproduction cost is liable to be increased because many unsaturatedcompounds including 2-methyleneadamantane are expensive.

When the acrylic acid compound of formula (1) is allowed to react withthe unsaturated compound of formula (2) or (3) by the process of thepresent invention, the acrylate compound of formula (4) can be producedwith an enhanced efficiency. Especially when an acrylic acid compoundrepresented by the following formula (38):

wherein R⁶ is a hydrogen atom, a fluorine atom, an alkyl group(preferably a C₁-C₄ straight-chain or branched alkyl group), an alkenylgroup (preferably a C₂-C₄ straight-chain or branched alkenyl group), afluoroalkyl group (preferably a C₁-C₄ straight-chain or branchedfluoroalkyl group), or a fluoroalkenyl group (preferably a C₂-C₄straight-chain or branched fluoroalkenyl group), is allowed to reactwith 2-methyleneadamantane represented by the following formula (37):

a methyladamantyl acrylate compound represented by the following formula(40) can be produced with greatly enhanced efficiency.

wherein R⁶ is the same as defined above for formula (38).

This makes a striking contrast with the conventional process wherein amethyladamantyl acrylate compound having a fluoroalkyl group such as2-methyl-2-adamantyl α-trifluoromethylacrylate (MAFAC) is produced in alow yield.

The reaction of the acrylic acid compound of formula (1) with theunsaturated compound of formula (2) or (3) can be carried out in-thepresence of a catalyst to more enhance the efficiency. The catalyst ispreferably an acidic catalyst, which includes, for example, hydrogenfluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, nitricacid, phosphoric acid, sulfonic acid compounds, carboxylic acidcompounds and Lewis acid compounds.

By the term “sulfonic acid compounds” used herein, we mean catalystshaving a sulfonic acid group in the molecule structure. The sulfonicacid compounds are not particularly limited provided that they have asulfonic acid group, and, as specific examples thereof, there can bementioned inorganic sulfonic acids such as sulfuric acid, fluorosulfonicacid and chlorosulfonic acid; aliphatic sulfonic acids such asmethanesulfonic acid, ethanesulfonic acid, propanesulfonic acid,allylsulfonic acid, butanesulfonic acid, pentanesulfonic acid,hexanesulfonic acid, heptanesulfonic acid, octanesulfonic acid,nonanesulfonic acid, decanesulfonic acid, dodecanesulfonic acid,tetradecanesulfonic acid and DL-camphor-10-sulfonic acid; substitutedaliphatic sulfonic acids such as trifluoromethanesulfonic acid,aminomethanesulfonic acid, 2-bromoethanesulfonic acid,2-(N-morpholino)ethanesulfonic acid,N,N′-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid,N-(acetamido)-2-aminoethanesulfonic acid,N-2-hydroxyethylpiperazine-N′-2-ethanesulfonic acid,N-cyclohexyl-2-aminoethanesulfonic acid, 3-aminopropanesulfonic acid,N-cyclohexyl-2-hydroxy-3-aminopropanesulfonic acid,3-chloro-2-hydroxypropanesulfonic acid, 3-(N-morpholino)propanesulfonicacid, 2-hydroxy-3-morpholinopropanesulfonic acid,2-acrylamide-2-methylpropanesulfonic acid,2-amino-5-methylbenzene-1-sulfonic acid, methallylsulfonic acid andtaurine; aromatic sulfonic acids such as benzenesulfonic acid,p-chlorobenzenesulfonic acid, p-phenolsulfonic acid, guaiacol-4-sulfonicacid, p-styrenesulfonic acid, phenylhydrazine-p-sulfonic acid,1,2-benzenedisulfonic acid, 1,3-benzenedisulfonic acid,1,4-benzenedisulfonic acid, m-toluenesulfonic acid, p-toluenesulfonicacid, 2,4-dimethylbenzenesulfonic acid, 2,5-dimethylbenzenesulfonicacid, 2-mesitylenesulfonic acid, p-ethylbenzenesulfonic acid,3,5-dichloro-2-hydroxybenzenesulfonic acid, 2,4,6-trinitrobenzenesulfonic acid, o-aminobenzenesulfonic acid,m-xylidine-6-sulfonic acid, 4-amino-2-methylbenzene-1-sulfonic acid,4-amino-5-methoxy-2-methylbenzenesulfonic acid,4-amino-2-chlorotoluene-5-sulfonic acid, 1-naphthalenesulfonic acid,2-naphthalenesulfonic acid, 2, 6-naphthalenedisulfonic acid,2,7-naphthalenedisulfonic acid, 1-naphthol-2-sulfonic acid,1-naphthol-4-sulfonic acid, 1-naphthol-8-sulfonic acid,2-naphthol-6-sulfonic acid, 2-naphthol-3,6-disulfonic acid,1-naphthylamine-4-sulfonic acid, 1-naphthylamine-6-sulfonic acid,1-naphthylamine-8-sulfonic acid, 2-naphthylamine-1-sulfonic acid,2-naphthylamine-6-sulfonic acid, 2,3-dihydroxynaphthalene-6-sulfonicacid, 2-amino-5-naphthol-7-sulfonic acid,8-amino-1-naphthol-3,6-disulfonic acid,8-aminonaphthalene-1,3,6-trisulfonic acid,8-anilino-1-naphthalenesulfonic acid,4,4′-diaminostilbene-2,2′-disulfonic acid,7-iodo-8-hydroxyquinoline-5-sulfonic acid, diphenylamine-4-sulfonicacid, 1-pyrenesulfonic acid and sulfanilic acid; and sulfonic acid typecation-exchange resins such as Nafion (available from Du Pont Co.),sulfonic acid type Amberlist (available from Rohm & Haas Co.), sulfonicacid type Amberlite (available from Rohm & Haas Co.), sulfonic acid typeDiaion (available from Mitsubishi Chem. Corp.), sulfonic acid typeDuolite (available from Sumitomo Chem. Co.), sulfonic acid type Dowex(available from Dow Chem. Co.), sulfonic acid type Purolite (availablefrom Purolite Co.) and sulfonic acid type Lewatit (available from BayerAG).

By the term “carboxylic acid compounds” used herein, we mean catalystshaving a carboxylic acid group in the molecule structure. The carboxylicacid compounds are not particularly limited provided that they have acarboxylic acid group, and, as specific examples thereof, there can bementioned aliphatic carboxylic acids such as formic acid, acetic acid,propionic acid, butyric acid, valeric acid, caproic acid, heptanoicacid, caprylic acid, pelargonic acid, capric acid, n-undecylenic acid,acrylic acid, crotonic acid, isocrotonic acid, vinylacetic acid,methacrylic acid, angelic acid, tiglic acid, 2-pentenoic acid,3-pentenoic acid, 4-pentenoic acid, α-ethylacrylic acid,β,β-dimethylacrylic acid, 2-hexenoic acid, 3-hexenoic acid, 4-hexenoicacid, 5-hexenoic acid, 2-methyl-2-pentenoic acid, 3-methyl-2-pentenoicacid, 4-methyl-2-pentenoicacid, 4-methyl-3-pentenoicacid, 2-heptenoicacid, 2-octenoic acid, 4-decenoic acid, 9-decenoic acid, 9-undecenoicacid, 10-undecenoic acid, 4-dodecenoic acid, 5-dodecenoic acid,propiolic acid, tetrolic acid, ethylpropiolic acid, n-propylpropiolicacid, isopropylpropiolic acid, n-butylpropiolicacid,t-butylpropiolicacid, n-amylpropiolicacid, 9-undecynoic acid,2,4-pentadienoic acid, 2,4-hexadienoic acid, fluoroacetic acid,difluoroacetic acid, trifluoroacetic acid, chloroacetic acid,dichloroacetic acid, trichloroacetic acid, bromoacetic acid,dibromoacetic acid, tribromoacetic acid, iodoacetic acid, diiodoaceticacid, triiodoacetic acid, α-chloropropionic acid, β-chloropropionicacid, α-bromopropionic acid, β-bromopropionic acid, α-iodopropionicacid, β-iodopropionic acid, α-chloroacrylic acid, β-chloroacrylic acid,trichloroacrylic acid, α-bromoacrylic acid, β-bromoacrylic acid,α-iodoacrylic acid, β-iodoacrylic acid, α-chlorocrotonic acid,β-chlorocrotonic acid, γ-chlorocrotonic acid, α-bromocrotonic acid,β-bromocrotonic acid, γ-bromocrotonic acid, oxalic acid, malonic acid,succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid,azelaic acid, sebacic acid, chloromalonic acid, dichloromalonic acid,bromomalonic acid, dibromomalonic acid, chlorosuccnic acid,dichlorosuccnic acid, bromosuccnic acid, dibromosuccnic acid,methylsuccnic acid, methylenemalonic acid, α-methylglutaric acid,β-methylglutaric acid, maleic acid, fumaric acid, itaconic acid,citraconic acid, mesaconic acid, glutaconic acid, trans-transmuconicacid, cis-cismuconic acid, cis-transmuconic acid, acetylenedicarboxylicacid, 1-propylene-1,3-dicarboxylic acid, 1-butyne-1,4-dicarboxylic acid,2-butyne-1,4-dicarboxylic acid, propane-1,2,3-tricarboxylic acid andbutane-1,2,3,4-tetracarboxylic acid; and aromatic carboxylic acids suchas benzoic acid, o-hydroxybenzoic acid, m-hydroxybenzoic acid,p-hydroxybenzoic acid, 4-acetylbenzoic acid, o-fluorobenzoic acid,phthalic acid, 1,2,4,5-benzenetetracarboxylic acid, 1-naphthoic acid,2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 4-biphenylcarboxylic acid,4,4′-biphenyldicarboxylic acid, 9-anthracenedicarboxylic acid,2-quinolinecarboxylic acid and 4-pyridinecarboxylic acid.

As specific examples of the Lewis acid compounds used as a catalyst inthe present invention, there can be mentioned boron trifluoride,borontrichloride, borontribromide, aluminumchloride, aluminum bromide,iron (III) chloride, iron (III) bromide, antimony trichloride, antimonypentachloride, titanium trichloride, titanium tetrachloride, zincchloride, zinc bromide, tin chloride, copper chloride, tungstenchloride, iron powder and zeolites.

Among the above-recited catalysts, sulfonic acid compounds such assulfuric acid and p-toluenesulfonic acid are preferable. Sulfuric acidis especially preferable in view of safety and cost.

The catalysts may be used either alone or as a mixture of at least twothereof.

The amount of the catalyst is not particularly limited, but is usuallyin the range of 10⁻⁴ mol to 1 mol per mol of the acrylic acid compoundof formula (1).

In a preferable example of the process of the present invention, anacrylate compound represented by the following formula (41):

wherein R⁶ is a hydrogen atom, a methyl group or a trifluoromethylgroup, and R²³ is 2-methyl-2-adamanthyl group or a 1-methylcyclohexylgroup, is produced by allowing an acrylic acid compound represented bythe following formula (38):

wherein R⁶ is the same as defined above for formula (41), to react with2-methyleneadamantane or 1-ethylcyclohexene, represented by thefollowing formula (37) or (36), respectively:

in the presence of an acid catalyst comprised of sulfuric acid orp-toluenesulfonic acid.

The reaction temperature is not particularly limited, but is usually inthe range of −50° C. to 100° C.

The process of the present invention can be carried out in the presenceof a solvent. The solvent used is not particularly limited, and, asspecific examples thereof, there can be mentioned aliphatic hydrocarbonssuch as hexane and heptane; aromatic hydrocarbons such as benzene,toluene and xylene; halogenated hydrocarbons such as dichloromethane anddichloroethane; and ethers such as diethyl ether and tetrahydrofuran.

After completion of the reaction, the residual raw materials andcatalyst are removed, for example, by washing a reaction mixture withwater, and the object acrylate compound can be obtained by conventionalpurification procedures such as distillation, recrystallization andcolumn chromatography.

The invention will now be specifically described by the followingexamples that by no means limit the scope of the invention.

REFERENCE EXAMPLE 1 Synthesis of 2-methyleneadamantane

One liter flask equipped with a Dean-Stark condenser was charged-with166.3 g (1.0 mol) of 2-methyl-2-adamantanol (supplied by Sigma-AldrichCo.), 2.0 g (20 mmol) of sulfuric acid and 500 g of toluene. The contentwas heated to the solvent reflux temperature. While toluene and waterproduced through the reaction were collected as an azeotrope by theDean-Stark condenser, the reaction mixture was refluxed for 2 hours.After completion of the reaction, the catalyst was removed by washingthe reaction mixture with water and the obtained organic phase wasconcentrated to dryness to give 152.5 g of white solid2-methyleneadamantane (purity: 99.0%, yield: 98.0%).

EXAMPLE 1 Synthesis of 2-methyl-2-adamantyl α-trifluoromethylacrylate[MAFAC]

A 500 ml flask was flushed with nitrogen to displace the air withnitrogen, and was charged with 70.0 g (0.50 mol) ofa-trifluoromethylacrylic acid (supplied from Tosoh F-tech Inc.), 1.0 g(10 mmol) of sulfuric acid and 100 g of toluene. Separately 88.8 g (0.60mol) of 2-methyleneadamantane, prepared by the same procedures asdescribed in Reference Example 1, was dissolved in 100 g of toluene. Theobtained solution of 2-methyleneadamantane in toluene was dropwise addedto the content in the flask over a period of about 3 hours, while thecontent was maintained at a reaction temperature of about 5° C. Then thecontent was stirred for 15 hours at the same temperature. Aftercompletion of the reaction, the residual catalyst was neutralized byadding 40.0 g (50 mmol) of a 5% aqueous sodium hydroxide solution, andthe neutralized liquid was washed with an aqueous saturated sodiumchloride solution. The thus-obtained organic phase was subjected tocolumn chromatography, and further, analyzed by NMR and massspectrometry. Thus, 133.9 g (yield: 93.0%) of the object2-methyl-2-adamantyl α-trifluoromethylacrylate was obtained.

Results of analysis:

-   -   (1) ¹H-NMR (CDCl₃):    -   δ (ppm)=6.73(1H,S), 6.42(1H,S), 1.63-2.43(15H,m)    -   (2) MS spectrum (m/z): 288(M+)

EXAMPLE 2 Synthesis of 2-methyl-2-adamantyl acrylate [MAAC]

A 500 ml flask was flushed with nitrogen to displace the air withnitrogen, and was charged with 36.0 g (0.50 mol) of acrylic acid, 0.5g(5mmol) of sulfuric acid and 100 g of toluene. Separately 88.8 g (0.60mol) of 2-methyleneadamantane, prepared by the same procedures asdescribed in Reference Example 1, was dissolved in 100 g of toluene. Theobtained solution of 2-methyleneadamantane in toluene was dropwise addedto the content in the flask over a period of about 3 hours, while thecontent was maintained at a reaction temperature of about 20° C. Thenthe content was stirred for 5 hours at the same temperature. Aftercompletion of the reaction, the residual catalyst was neutralized byadding 40.0 g (50 mmol) of a 5% aqueous sodium hydroxide solution, andthe neutralized liquid was washed with an aqueous saturated sodiumchloride solution. The thus-obtained organic phase was subjected tocolumn chromatography, and further, analyzed by NMR and massspectrometry. Thus, 100.7 g (yield: 91.5%) of the object2-methyl-2-adamantyl acrylate was obtained.

EXAMPLE 3 Synthesis of 2-methyl-2-adamantyl methacrylate [MAMC]

A 500 ml flask was flushed with nitrogen to displace the air withnitrogen, and was charged with 43.0 g (0.50 mol) of methacrylic acid,0.95 g (5 mmol) of p-toluenesulfonic acid monohydrate (supplied by WakoPure Chem. Ind. Ltd.) and 100 g of toluene. Separately 74.0 g (0.50 mol)of 2-methyleneadamantane, prepared by the same procedures as describedin Reference Example 1, was dissolved in 100 g of toluene. The obtainedsolution of 2-methyleneadamantane in toluene was dropwise added to thecontent in the flask over a period of about 3 hours, while the contentwas maintained at a reaction temperature of about 5° C. Then the contentwas stirred for 5 hours at the same temperature. After completion of thereaction, the residual catalyst was neutralized by adding 40.0 g (50mmol) of a 5% aqueous sodium hydroxide solution, and the neutralizedliquid was washed with an aqueous saturated sodium chloride solution.The thus-obtained organic phase was subjected to column chromatography,and further, analyzed by NMR and mass spectrometry. Thus, 106.2 g(yield: 90.8%) of the object 2-methyl-2-adamantyl methacrylate wasobtained.

REFERENCE EXAMPLE 2 Synthesis of 1-ethylcyclohexanol

One liter flask was flushed with nitrogen to displace the air withnitrogen, and was charged with 26.7 g (1.1 mol) of metallic magnesium(supplied by Aldrich Co.) and 500 g of tetrahydrofuran. Among 109.0 g(1.0 mol) of ethyl bromide (supplied by Kanto Chem. Co.), about 5 gthereof was added to the content in the flask to confirm heat generationdue to initiation of the exothermic Grignard reaction, and then theremainder of ethyl bromide was dropwise added over a period of about 1hour while the inner temperature was controlled so as not to exceed 50°C. Further, the reaction mixture was stirred at the same temperature for1 hour. Then, 98.2 g (1.0 mol) of cyclohexanone was dropwise added overa period of about 3 hours while the reaction temperature was controlledso as not to exceed 20° C. Further, the reaction mixture was stirred atthe same temperature for 1 hour. After completion of the reaction, thereaction mixture was treated with 550 g (1.5 mol) of an aqueous HClsolution and the obtained organic phase was concentrated to dryness togive 127.6 g of a white solid. NMR and mass spectroscopy of the whitesolid revealed that it was 1-ethylcyclohexanol (purity: 98.5%, yield:98.0%).

REFERENCE EXAMPLE 3 Synthesis of 1-ethylcyclohexene

One liter flask equipped with a Dean-Stark condenser was charged with64.1 g (0.5 mol) of 1-ethylcyclohexanol, prepared in Reference Example2, 1.0 g (10 mmol) of sulfuric acid and 300 g of toluene. The contentwas heated to the solvent reflux temperature. While toluene and waterproduced through the reaction were collected as an azeotrope by theDean-Stark condenser, the reaction mixture was refluxed for 1 hours.After completion of the reaction, the catalyst was removed by washingthe reaction mixture with water and the obtained organic phase wasdistilled under reduced pressure to obtain 58.3 g of colorless liquid asa fraction of 77° C./15 kPa. NMR and mass spectroscopy of the colorlessliquid revealed that it was 1-ethylcyclohexene (purity: 96.0%, yield:87.5%).

EXAMPLE 4 Synthesis of 1-ethylcyclohexyl methacrylate

A 500 ml flask was flushed with nitrogen to displace the air withnitrogen, and was charged with 43.0 g (0.5 mol) of methacrylic acid, 0.5g (5 mmol) of sulfuric acid and 100 g of toluene. Separately 110.2 g(1.0 mol) of 1-ethylcyclohexene, prepared by the same procedures asdescribed in Reference Example 3, was dissolved in 100 g of toluene. Theobtained solution of 1-ethylcyclohexene in toluene was dropwise added tothe content in the flask over a period of about 3 hours, while thecontent was maintained at a reaction temperature of about 30° C. Thenthe content was stirred for 15 hours at the same temperature. Aftercompletion of the reaction, the residual catalyst was neutralized byadding 40.0 g (50 mmol) of a 5% aqueous sodium hydroxide solution, andthe neutralized liquid was washed with an aqueous saturated sodiumchloride solution. The thus-obtained organic phase was subjected tocolumn chromatography, and further, analyzed by NMR and massspectrometry. Thus, 68.6 g (yield: 69.9%) of the object1-ethylcyclohexyl methacrylate was obtained.

Results of analysis:

-   -   (1) ¹H-NMR (CDCl₃):    -   δ (ppm)=6.12(1H,S), 5.55(1H,S), 1.25-2.37(15H,m), 0.89(3H,t)    -   (2) MS spectrum (m/z): 196(M+)

COMPARATIVE EXAMPLE 1 Synthesis of 2-methyl-2-adamantylα-trifluoromethylacrylate [MAFAC] from 2-methyl-2-adamantanol andα-trifluoromethylacryloyl chloride

A 500 ml flask was flushed with nitrogen to displace the air withnitrogen, and was charged with 83.1 g (0.50 mol) of2-methyl-2-adamantanol, 101.2 g (1.0 mol) of triethylamine and 200 g oftetrahydrofuran. Then 118.9 g (0.75 mol) of a -trifluoromethylacryloylchloride was dropwise added to the content in the flask over a period ofabout 1 hour, while the content was maintained at a reaction temperatureof about 0° C. Then the content was stirred for 10 hours at roomtemperature. After completion of the reaction, the reaction mixture waswashed with water and then with an aqueous saturated sodium chloridesolution. The thus-obtained organic phase was subjected to columnchromatography, and further, analyzed by NMR and mass spectrometry.Thus, 101.2 g (yield: 70.3%) of the object 2-methyl-2-adamantylα-trifluoromethylacrylate was obtained.

1-11. (canceled)
 12. A process for preparing an acrylate compoundrepresented by the following formula (4):

wherein R¹ and R² independently represent a hydrogen atom or a fluorineatom, R³ represents a hydrogen atom, a fluorine atom, an alkyl group, analkenyl group, a fluoroalkyl group or a fluoroalkenyl group, R⁴ and R⁵independently represent a hydrogen atom, a halogen atom, an alkyl group,an alkenyl group, a halogenated alkyl group, or a halogenated alkenylgroup, and X and Y independently represent a hydrocarbon group, whichmay have at least one substituent selected from the group consisting ofa halogen-containing substituent, an oxygen-containing substituent and anitrogen-containing substituent, and dashed line means that X and Y maybe bonded together to form a cyclic structure; which comprises allowingan acrylic acid compound represented by the following formula (1):

wherein R¹, R² and R³ are the same as defined above for formula (4), toreact with an unsaturated compound represented by the following formula(2) or (3):

wherein R⁴, R⁵, X and Y are the same as defined above for formula (4),and wherein the reaction of the acrylic acid compound of formula (1)with the unsaturated compound of formula (2) or (3) is carried out inthe presence of a catalyst.
 13. The process according to claim 12,wherein the catalyst is an acidic catalyst.
 14. The process according toclaim 13, wherein the acidic catalyst is a sulfonic acid groupcontaining catalyst.
 15. The process according to claim 14, wherein thesulfonic acid group-containing catalyst is sulfuric acid. 16-19.(canceled)